CN110364615B - Graphene oxide/molybdenum disulfide composite thermoelectric material and preparation method thereof - Google Patents
Graphene oxide/molybdenum disulfide composite thermoelectric material and preparation method thereof Download PDFInfo
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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Abstract
The invention provides a preparation method of a graphene oxide/molybdenum disulfide composite thermoelectric material, which comprises the following steps: s1) mixing graphene oxide and molybdenum disulfide nano-sheets in water, and performing ultrasonic treatment to obtain a mixed system; s2) coating the mixed system on a substrate, and drying at a low temperature to obtain a graphene oxide/molybdenum disulfide composite thermoelectric material; or filtering the mixed system to obtain the graphene oxide/molybdenum disulfide composite thermoelectric material. Compared with the prior art, the energy filtering effect in the obtained composite thermoelectric material can be improved by adding the vulcanized rice nano sheet into the graphene oxide nano sheet, the electric conductivity of the composite material can be continuously maintained, the heat conductivity can be reduced, the Seebeck coefficient of the composite thermoelectric material is improved, and the ZT value of the composite thermoelectric material is greatly increased; and the graphene oxide/molybdenum disulfide composite thermoelectric material has adjustable P-N type thermoelectric characteristics.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials and devices, and particularly relates to a graphene oxide/molybdenum disulfide composite thermoelectric material and a preparation method thereof.
Background
The thermoelectric material is a material capable of realizing direct conversion of heat energy and electric energy, and the thermoelectric power generation device and the refrigeration device based on the thermoelectric material have the characteristics of compact equipment structure, no noise and no pollution during operation, recycling of waste energy and the like, and have wide application prospects in the fields of military, medicine, aerospace, microelectronics, household appliances and the like. Compared with commercial block thermoelectric materials, the flexible thermoelectric material has the unique advantages of flexibility, low preparation cost, simple process, wide application range and the like, and attracts more and more attention in scientific research and enterprise in recent years.
The graphene oxide nano lamellar structure surface has a plurality of hydrophilic groups which can be uniformly dispersed in water, and meanwhile, as the lamellar structure has a plurality of empty positions, the scattering of phonons at the defect positions can be greatly improved, so that the thermal conductivity of the graphene oxide nano lamellar structure is effectively reduced. The properly reduced graphene oxide has higher carrier concentration and carrier mobility, and is suitable for preparing flexible thermoelectric materials. However, the mobility of electrons and holes of the reduced graphene is almost the same, so that the Seebeck coefficient of the reduced graphene is very low.
In order to improve the Seebeck coefficient of the reduced graphene, it may be composited with a conductive polymer or an inorganic semiconductor material. However, the composite thermoelectric material based on the reduced graphene is a block material formed by simply compositing conductive polymers or inorganic semiconductors with the reduced graphene, effective matching of composite components is not realized, and the defects of low seebeck coefficient, narrow application temperature range, no flexibility and the like still exist.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a graphene oxide/molybdenum disulfide composite thermoelectric material and a preparation method thereof, wherein the graphene oxide/molybdenum disulfide prepared by the method has an ultrahigh Seebeck coefficient, excellent electric conductivity and a lower heat conductivity.
The invention provides a preparation method of a graphene oxide/molybdenum disulfide composite thermoelectric material, which is characterized by comprising the following steps:
s1) mixing graphene oxide and molybdenum disulfide nano-sheets in water solution, and performing ultrasonic treatment to obtain a mixed system;
s2) coating the mixed system on a substrate, and drying at low temperature to obtain a graphene oxide/molybdenum disulfide composite thermoelectric material film;
or filtering the mixed system to obtain the graphene oxide/molybdenum disulfide composite thermoelectric material.
Preferably, the step S1) specifically includes:
mixing graphene oxide aqueous solution with molybdenum disulfide nanosheet aqueous solution, and performing ultrasonic treatment to obtain a mixed system;
the solid content of the graphene oxide aqueous solution is 5-20 mg/ml;
the solid content of the molybdenum disulfide nanosheet aqueous solution is 5-20 mg/ml.
Preferably, the graphene oxide aqueous solution is a graphene oxide aqueous solution obtained by a modified Hummers method; the molybdenum disulfide nanosheet aqueous solution is obtained by stripping molybdenum disulfide particles by using butyl lithium.
Preferably, the mass ratio of the graphene oxide to the molybdenum disulfide nanosheets is (2-9): (8-1).
Preferably, when the mass ratio of the graphene oxide to the molybdenum disulfide nanosheets is less than or equal to 1, the obtained graphene oxide/molybdenum disulfide composite thermoelectric material is a P-type thermoelectric material.
Preferably, the crystal phase transition temperature of the P-type thermoelectric material is 323K-343K; seebeck coefficient at the crystal phase transition point is 50000-80000 μV/K.
Preferably, when the mass ratio of the graphene oxide to the molybdenum disulfide nanosheets is greater than 1, the obtained graphene oxide/molybdenum disulfide composite thermoelectric material is an N-type thermoelectric material.
Preferably, the crystalline phase transition temperature of the N-type thermoelectric material is 323K-343K; seebeck coefficient is-25000 to-35000 mu V/K at the crystal phase transition point.
Preferably, the ultrasonic treatment time is 10-30 min; the substrate is a flexible substrate.
The invention also provides a graphene oxide/molybdenum disulfide composite thermoelectric material, which is obtained by compositing a graphene oxide sheet layer and a molybdenum disulfide nano sheet layer.
The invention provides a preparation method of a graphene oxide/molybdenum disulfide composite thermoelectric material, which comprises the following steps: s1) mixing graphene oxide and molybdenum disulfide nano-sheets in water, and performing ultrasonic treatment to obtain a mixed system; s2) coating the mixed system on a substrate, and drying at a low temperature to obtain a graphene oxide/molybdenum disulfide composite thermoelectric material; or filtering the mixed system to obtain the graphene oxide/molybdenum disulfide composite thermoelectric material. Compared with the prior art, the energy filtering effect in the obtained composite thermoelectric material can be improved by adding the vulcanized rice nano sheet into the graphene oxide nano sheet, and the electric conductivity of the composite material can be maintained and the heat conductivity can be reduced, so that the Seebeck coefficient of the composite thermoelectric material is improved, and the ZT value of the composite thermoelectric material is greatly increased; the graphene oxide/molybdenum disulfide composite thermoelectric material has adjustable P-N type thermoelectric characteristics, the P-N characteristics of the composite material can be adjusted by adjusting the content of graphene oxide in the composite material, meanwhile, the composite thermoelectric material has good strength, flexibility and conductivity, the thickness is controllable, the shape is tailorable, the preparation method is simple, the operation is easy, the preparation cost is low, and the composite thermoelectric material is suitable for the fields of thermoelectric generation, solar batteries, energy storage, sensing and conductive composite materials.
Experiments show that the graphene oxide/molybdenum disulfide composite thermoelectric material prepared by the method can work under a relatively low temperature condition (243K-373K). When the obtained graphene oxide/molybdenum disulfide composite thermoelectric material is in an N-type characteristic, the highest value of the Seebeck coefficient in a temperature range of 243K-373K can reach-30000 mu V/K; seebeck coefficient is-3000 to-9000 mu V/K under room temperature; the conductivity at room temperature is 100-1000S/m; the heat conductivity is 0.96-1.27W/mK; when the prepared graphene oxide/molybdenum disulfide composite thermoelectric material is in a P type characteristic, the highest value of the Seebeck coefficient in a temperature range of 243K-373K can reach 72000 mu V/K; under the room temperature condition, the Seebeck coefficient is 1000-5000 mu V/K; the conductivity at room temperature is 1000-3000S/m.
Drawings
FIG. 1 is a scanning electron micrograph of a thermoelectric film of the composite material obtained in example 3 of the present invention;
FIG. 2 is a transmission electron micrograph of a thermoelectric film of the composite material obtained in example 3 of the present invention;
FIG. 3 is a graph showing the relationship between the planar thermal conductivity and the temperature of the thermoelectric thin film of the composite material obtained in example 3 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a graphene oxide/molybdenum disulfide composite thermoelectric material, which is obtained by compounding a graphene oxide sheet layer and a molybdenum disulfide nano sheet layer.
According to the invention, the sulfide nano-sheet layer is added into the graphene oxide nano-sheet layer, so that the energy filtering effect in the composite thermoelectric material can be improved, the electric conductivity of the composite material can be maintained, and the electric conductivity can be reduced to be lower than the heat conductivity, thereby improving the Seebeck coefficient of the composite thermoelectric material, and further greatly increasing the ZT value of the composite thermoelectric material.
Wherein, the mass ratio of the graphene oxide lamellar to the molybdenum disulfide nanosheet layer is preferably (2-9): (8-1), more preferably (1-4): (4-1); when the mass ratio of the graphene oxide to the molybdenum disulfide is greater than 1, the graphene oxide/molybdenum disulfide composite thermoelectric material is an N-type thermoelectric material; the crystal phase transition temperature of the N-type thermoelectric material is preferably 323K-343K; the highest Seebeck coefficient at the crystal phase transition point is preferably-25000 to-35000. Mu.V/K, more preferably-30000. Mu.V/K; the room temperature Seebeck coefficient is preferably-3000 to-9000 mu V/K; the room temperature conductivity is preferably 100 to 1000S/m. When the mass ratio of the graphene oxide sheet layer to the molybdenum disulfide nano sheet layer is smaller than or equal to 1, the graphene oxide/molybdenum disulfide composite thermoelectric material is a P-type thermoelectric material; the crystal phase transition temperature interval of the P-type thermoelectric material is preferably 323K-343K; the highest Seebeck coefficient at the crystal phase transition point is preferably 50000 to 80000. Mu.V/K, more preferably 60000 to 80000. Mu.V/K, still more preferably 72 000. Mu.V/K; the Seebeck coefficient at room temperature is preferably 1000-5000 mu V/K; the room temperature conductivity is preferably 1000-3000S/m;
according to the invention, the graphene oxide is added into the composite thermoelectric material, so that the thermal conductivity of the composite thermoelectric material can be reduced, compared with the thermal conductivity (30-40W/mK) of molybdenum disulfide, the in-plane thermal conductivity of the graphene oxide/molybdenum disulfide composite thermoelectric material is only 0.96-1.27W/mK, and the lower thermal conductivity can obviously improve the ZT value of the composite thermoelectric material and improve the energy conversion efficiency; in addition, the interface influence of the graphene oxide and molybdenum disulfide can be introduced by introducing the graphene oxide, so that the forbidden band width (band gap), the interlayer spacing and the distribution of internal electron clouds of the composite thermoelectric material are changed, and the thermoelectric material with high Seebeck coefficient is obtained.
The invention also provides a preparation method of the graphene oxide/molybdenum disulfide composite thermoelectric material, which comprises the following steps: s1) mixing graphene oxide and molybdenum disulfide nano-sheets in water, and performing ultrasonic treatment to obtain a mixed system; s2) coating the mixed system on a substrate to obtain a graphene oxide/molybdenum disulfide composite thermoelectric material film; or filtering the mixed system to obtain the graphene oxide/molybdenum disulfide composite thermoelectric material.
The invention is not particularly limited in the source of all raw materials, and can be commercially available or self-made.
In the present invention, it is preferable to mix the graphene oxide aqueous solution with the molybdenum disulfide nanosheet aqueous solution.
The solid content of the graphene oxide aqueous solution is preferably 10-20 mg/ml; the graphene oxide aqueous solution is preferably a graphene oxide aqueous solution obtained by a modified Hummers method; more preferably, the preparation is carried out according to the following steps: mixing graphite, concentrated sulfuric acid and sodium nitrate under ice bath condition, and slowly adding KMnO 4 Reacting, and then heating to 30-35 ℃ for reacting; slowly adding deionized water for reaction, and heating to 90-98 ℃ for reaction; deionized water at 100deg.C is added again, and 30% H is added after stirring reaction 2 O 2 Stirring to react, cooling to room temperature, and centrifuging to obtain graphene oxide aqueous solution with pH value of 5-7.
The solid content of the molybdenum disulfide nanosheet aqueous solution is preferably 10-20 mg/ml; the molybdenum disulfide nanosheet aqueous solution is preferably a molybdenum disulfide nanosheet aqueous solution obtained by stripping molybdenum disulfide particles by using butyl lithium, and is more preferably prepared according to the following steps: in a nitrogen protection atmosphere, mixing molybdenum disulfide and butyl lithium in normal hexane, stirring at room temperature for reaction, performing ultrasonic treatment under the ice bath condition, adding deionized water, performing high-speed centrifugal separation, and dialyzing the reaction product with the deionized water to obtain a molybdenum disulfide nanosheet aqueous solution; the particle size of the molybdenum disulfide is preferably 200-500 meshes.
After mixing, carrying out ultrasonic dispersion to obtain a mixed system; the power of the ultrasound is preferably 100-300W, more preferably 100-200W; the time of the ultrasonic treatment is preferably 10-30 min; the ultrasound is preferably carried out at room temperature.
Coating the mixed system on a substrate; the substrate is preferably a flexible substrate, more preferably a plastic film, fabric or paper; the substrate is preferably surface hydrophilized and then coated with the mixed system.
After being coated on a substrate, the graphene oxide/molybdenum disulfide composite thermoelectric material film is obtained after water is naturally volatilized and removed at room temperature; the graphene oxide/molybdenum disulfide composite thermoelectric material film can be obtained by freeze drying after naturally volatilizing at room temperature to remove moisture, so as to thoroughly remove moisture; the thickness of the graphene oxide/molybdenum disulfide composite thermoelectric material film is preferably 1-10 microns, more preferably 1-6 microns, still more preferably 1-4 microns, and most preferably 1-2 microns; the temperature of the freeze drying is preferably-30 ℃ to-40 ℃; the time for the freeze-drying is preferably 36 to 72 hours.
In the invention, the mixed system can be directly filtered to obtain the graphene oxide/molybdenum disulfide composite thermoelectric material; the filtration method is preferably vacuum filtration. Preferably filtering, and freeze-drying to thoroughly remove water to obtain graphene oxide/molybdenum disulfide composite thermoelectric material; the graphene oxide/molybdenum disulfide composite thermoelectric material can be obtained by freeze drying after direct freezing, and the obtained composite material has a porous structure and can be subjected to tabletting treatment; the thickness of the material obtained after the tabletting treatment is preferably 0.1 to 10mm, more preferably 0.5 to 5mm, still more preferably 1 to 2mm; the temperature of the freeze drying is preferably-30 ℃ to-40 ℃; the time for the freeze-drying is preferably 36 to 72 hours.
According to the invention, the vulcanized rice nano-sheets are added into the graphene oxide nano-sheets, so that the energy filtering effect in the obtained composite thermoelectric material can be improved, the electric conductivity of the composite material can be continuously maintained, the heat conductivity can be reduced, the Seebeck coefficient of the composite thermoelectric material is improved, and the ZT value of the composite thermoelectric material is greatly increased; the graphene oxide/molybdenum disulfide composite thermoelectric material has adjustable P-N type thermoelectric characteristics, the P-N characteristics of the composite material can be adjusted by adjusting the content of graphene oxide in the composite material, meanwhile, the composite thermoelectric material has good strength, flexibility and conductivity, the thickness is controllable, the shape is tailorable, the preparation method is simple, the operation is easy, the preparation cost is low, and the composite thermoelectric material is suitable for the fields of thermoelectric generation, solar batteries, energy storage, sensing and conductive composite materials.
In order to further illustrate the invention, the graphene oxide/molybdenum disulfide composite thermoelectric material and the preparation method thereof provided by the invention are described in detail below with reference to examples.
The reagents used in the examples below are all commercially available.
Example 1
Preparation of graphene oxide: under ice bath, adding 5g of graphite powder with the size of 300 meshes into 130mL of concentrated sulfuric acid with the concentration of more than 98%, uniformly stirring after adding 2.5g of sodium nitrate, slowly adding 15g of potassium permanganate under mechanical stirring, heating to 30 ℃ after continuous stirring for 2 hours, and continuously stirring for 0.5 hour. 230ml of deionized water was then slowly added dropwise and stirred for 0.5 hours. Heating to 95 ℃, adding 350ml of deionized water with the temperature of 100 ℃ and stirring for 10 minutes. Dropwise adding 5-2 mL of H with concentration of 30% 2 O 2 Stirring for 20 minutes. And (3) after the temperature is reduced to room temperature, carrying out high-speed centrifugal separation on the obtained yellow brown solution to remove impurities such as residual metal salts and the like, and obtaining yellow brown graphene oxide dispersion liquid with the pH value of 5-7 after centrifugal separation for multiple times, wherein the solid content of graphene oxide is 5-20%.
Example 2
Nanometer lamellar structure MoS 2 Is prepared from the following steps: 1g of MoS with 300-500 meshes is taken and added 2 Placing the mixture in a glass reactor with a rubber plug, and then introducing nitrogen into the reactor to remove air in the reactor. 10ml of an n-butyllithium/n-hexane solution having a molar concentration of 1.6mol/L was slowly added while keeping the reactor closed. Stirring at room temperature for 2 days to obtain Li x MoS 2 An intermediate; then placing the reaction system in an ice bath for ultrasonic treatment for 1 hour, and slowly adding 20ml of deionized water; subjecting the solution after the reaction to high-speed centrifugation to remove n-hexane and other impurities; finally, the reaction product is placed in a dialysis bag, deionized water is adopted for dialysis for 2 days to obtain the required molybdenum disulfide nanosheet aqueous solution,MoS in the final product 2 The solid content of (2) is 5-20%.
Example 3
10ml of the graphene oxide solution obtained in example 1 (preferably having a solid content of 10 mg/ml) was removed and placed in a 100ml beaker, and then the MoS obtained in example 2 was added 2 2.5ml of a solution (solid content 10 mg/ml) in which graphene oxide and MoS were oxidized 2 The mass ratio of (2) is 4:1. Ultrasonic treatment (ultrasonic power is 100W) for 10 min at room temperature to obtain graphene oxide and MoS 2 Is uniformly mixed with the nano-sheet layer. And then uniformly coating the obtained mixed solution on aramid paper (the thickness of the coating film is 80 microns) by adopting a film coater, and volatilizing water in a room temperature environment to obtain the required composite material thermoelectric film, wherein the thickness of the film is about 1 micron. The prepared composite material film is placed in a refrigerator with the temperature of 4 ℃ for storage.
The composite thermoelectric film obtained in example 3 was tested by a four-probe method to obtain a conductivity of about 135S/m.
The composite thermoelectric film obtained in example 3 was tested using a thermoelectric testing apparatus (TEP 600,Seepel instrument) to give a room temperature Seebeck coefficient of-3410. Mu.V/K.
Testing the thermoelectric film of the composite material obtained in the example 3 by using a variable-temperature X-ray diffraction method and a differential scanning calorimetry (the testing temperature range is-30 ℃ to 100 ℃), and obtaining a crystal phase transition temperature interval of molybdenum disulfide in a composite material system of about 323 to 343K; the Seebeck coefficient of the hot spot film of the composite material at the crystal orientation transition point is-29000 mu V/K.
The thermoelectric thin film of the composite material obtained in example 3 was examined by a scanning electron microscope, and a scanning electron micrograph thereof was obtained as shown in fig. 1. From FIG. 1, it can be seen that graphene oxide and MoS 2 Surface morphology of the composite film.
The composite thermoelectric film obtained in example 3 was examined by transmission electron microscopy to obtain a transmission electron micrograph thereof, as shown in fig. 2. From FIG. 2, it can be seen that graphene oxide and MoS 2 Composite sheet structure.
By means of Hot DThe composite thermoelectric film obtained in example 3 was examined by a isk thermal constant analyzer to obtain a curve of the planar thermal conductivity versus temperature, as shown in fig. 3. From FIG. 3, it can be seen that graphene oxide and MoS 2 The plane heat conductivity coefficient of the composite material is 0.96-1.27W/mK.
Example 4
10ml of the graphene oxide solution obtained in example 1 (preferably having a solid content of 10 mg/ml) was removed and placed in a 100ml beaker, and then the MoS obtained in example 2 was added 2 40ml of a solution (solid content 10 mg/ml) in which graphene oxide and MoS were present 2 The mass ratio of (2) is 1:4. Ultrasonic treatment (ultrasonic power is 100W) for 10 min at room temperature to obtain graphene oxide and MoS 2 Is uniformly mixed with the nano-sheet layer. And then uniformly coating the obtained mixed solution on aramid paper (the thickness of a coating film is 80 microns) by adopting a film coater, and volatilizing water in a room temperature environment to obtain the required composite material thermoelectric film, wherein the thickness of the film is about 2 microns.
The composite thermoelectric film obtained in example 4 was tested by the four-probe method, resulting in a conductivity of about 1800S/m.
The composite thermoelectric film obtained in example 4 was tested using a thermoelectric test instrument (tep.600, seepel instrument) to give a room temperature Seebeck coefficient of 1596 μv/K.
Testing the thermoelectric thin film of the composite material obtained in the embodiment 3 by using a variable-temperature X-ray diffraction method and a differential scanning calorimetry method to obtain a crystal phase transition temperature interval of molybdenum disulfide in a composite material system of about 323-343K; the Seebeck coefficient of the composite material hot spot film at the crystal orientation transition point is 71957 mu V/K.
Example 5
10ml of the graphene oxide solution obtained in example 1 (preferably having a solid content of 10 mg/ml) was removed and placed in a 100ml beaker, and then the MoS obtained in example 2 was added 2 10ml of a solution (solid content 10 mg/ml) in which graphene oxide and MoS were present 2 The mass ratio of (2) is 1:1. Ultrasonic treatment (ultrasonic power is 100W) for 10 min at room temperature to obtain graphene oxide and MoS 2 Is uniformly mixed with the nano-sheet layer. Then using a film coaterThe obtained mixed solution is uniformly coated on aramid paper (the thickness of a coating film is 80 microns), and the required composite material thermoelectric film can be obtained after the water is volatilized in the room temperature environment, wherein the thickness of the film is about 1 micron.
The composite thermoelectric film obtained in example 5 was tested by the four-probe method to obtain a conductivity of about 1620S/m.
The composite thermoelectric film obtained in example 5 was tested using a thermoelectric test instrument (tep.600, seepel instrument) to give a room temperature Seebeck coefficient of 2384 μv/K.
Testing the thermoelectric thin film of the composite material obtained in the example 5 by using a variable-temperature X-ray diffraction method and a differential scanning calorimetry method to obtain a crystal phase transition temperature interval of molybdenum disulfide in a composite material system of about 323-343K; the Seebeck coefficient of the composite thermoelectric film at the crystal orientation transition point is about 55442 μV/K.
Example 6
10ml of the graphene oxide solution obtained in example 1 (preferably having a solid content of 10 mg/ml) was removed and placed in a 100ml beaker, and then the MoS obtained in example 2 was added 2 10ml of a solution (solid content 10 mg/ml) in which graphene oxide and MoS were present 2 The mass ratio of (2) is 1:1. Ultrasonic treatment (ultrasonic power is 100W) for 10 min at room temperature to obtain graphene oxide and MoS 2 Is uniformly mixed with the nano-sheet layer. And then the mixed solution is frozen in a refrigerator with the temperature of minus 10 ℃ for 12 hours, and then the frozen graphene oxide/molybdenum disulfide/water composite system is placed in a freeze dryer for vacuum freeze drying, wherein the freeze drying temperature is minus 30 ℃ and the drying time is 48 hours. And obtaining the P-type graphene oxide/molybdenum disulfide composite thermoelectric material with a porous structure.
100mg of the P-type graphene oxide/molybdenum disulfide composite thermoelectric material having a porous structure in example 6 was mechanically pressed (preferably under a pressure of 10 tons) to obtain a composite sheet having a thickness of about 1 mm.
The composite thermoelectric film obtained in example 6 was tested by a four-probe method to obtain a conductivity of about 1780S/m.
The composite obtained in example 6 was tested using a thermoelectric testing instrument (TEP.600, seepel instrument) to give a room temperature Seebeck coefficient of 2384. Mu.V/K.
Claims (8)
1. The preparation method of the graphene oxide/molybdenum disulfide composite thermoelectric material is characterized by comprising the following steps of:
s1) mixing graphene oxide and molybdenum disulfide nano-sheets in water solution, and performing ultrasonic treatment to obtain a mixed system;
s2) coating the mixed system on a substrate, and drying at low temperature to obtain a graphene oxide/molybdenum disulfide composite thermoelectric material film;
or filtering the mixed system to obtain a graphene oxide/molybdenum disulfide composite thermoelectric material;
the step S1) specifically comprises the following steps:
mixing graphene oxide aqueous solution with molybdenum disulfide nanosheet aqueous solution, and performing ultrasonic treatment to obtain a mixed system;
the solid content of the graphene oxide aqueous solution is 5-20 mg/ml;
the solid content of the molybdenum disulfide nanosheet aqueous solution is 5-20 mg/ml;
the mass ratio of the graphene oxide to the molybdenum disulfide nanosheets is (2-9): (8-1).
2. The preparation method of claim 1, wherein the graphene oxide aqueous solution is a graphene oxide aqueous solution obtained by a modified Hummers method; the molybdenum disulfide nanosheet aqueous solution is obtained by stripping molybdenum disulfide particles by using butyl lithium.
3. The preparation method of claim 1, wherein the graphene oxide/molybdenum disulfide composite thermoelectric material is a P-type thermoelectric material when the mass ratio of the graphene oxide to the molybdenum disulfide nanosheets is less than or equal to 1.
4. The method according to claim 3, wherein the P-type thermoelectric material has a crystal phase transition temperature of 323K to 343K; seebeck coefficient at the crystal phase transition point is 50000-80000 μV/K.
5. The preparation method of claim 1, wherein when the mass ratio of the graphene oxide to the molybdenum disulfide nanosheets is greater than 1, the obtained graphene oxide/molybdenum disulfide composite thermoelectric material is an N-type thermoelectric material.
6. The method according to claim 5, wherein the N-type thermoelectric material has a crystal phase transition temperature of 323K to 343K; seebeck coefficient is-25000 to-35000 mu V/K at the crystal phase transition point.
7. The method according to claim 1, wherein the time of the ultrasonic wave is 10 to 30 minutes; the substrate is a flexible substrate.
8. A graphene oxide/molybdenum disulfide composite thermoelectric material prepared by the preparation method of any one of claims 1 to 7, which is characterized by being obtained by compositing graphene oxide sheets and molybdenum disulfide nano sheets.
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| CN104733604A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院上海硅酸盐研究所 | Composite thermoelectric material and preparing method thereof |
| CN105591088A (en) * | 2016-03-22 | 2016-05-18 | 北京科技大学 | Lithium ion battery cathode material and preparing method thereof |
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| CN102142551A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene nano sheet/MoS2 composite nano material and synthesis method thereof |
| CN104137282A (en) * | 2011-12-30 | 2014-11-05 | 三星电子株式会社 | Heterogeneous laminate including graphene, and thermoelectric material, thermoelectric module, and thermoelectric apparatus including the heterogeneous laminate |
| CN102796590A (en) * | 2012-08-24 | 2012-11-28 | 江苏大学 | Preparation method for tubular graphene/MoS2 nanocomposite material |
| CN104733604A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院上海硅酸盐研究所 | Composite thermoelectric material and preparing method thereof |
| CN105591088A (en) * | 2016-03-22 | 2016-05-18 | 北京科技大学 | Lithium ion battery cathode material and preparing method thereof |
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